31351-12-9Relevant articles and documents
What Is the True Structure of D609, a Widely Used Lipid Related Enzyme Inhibitor?
Kato, Mikako,Hammam, Mostafa A. S.,Taniguchi, Tohru,Suga, Yoshiko,Monde, Kenji
supporting information, p. 768 - 771 (2016/03/01)
(Chemical Equation Presented) D609 (1) has been used as a lipid-related enzyme inhibitor during the past three decades. Although it has eight possible stereoisomers, no systematic research considering its chirality has been performed. In this paper, eight possible chiral alcohols as direct precursors of D609 were synthesized, and their stereochemistries were elucidated by a vibrational circular dichroism (VCD) technique. Phosphatidylcholine-specific phospholipase C and sphingomyelin synthase inhibition assays of these isomers showed considerable differences in their activities.
Photochemistry of aliphatic thioketones in the gas phase
Morrison, Harry,Lu, Yuelie,Carlson, Dean
, p. 5421 - 5432 (2007/10/03)
The solution and gas-phase photophysical and photochemical properties of a series of bicyclic and alicyclic thioketones (apothiocamphor (1), thiocamphor (2), thiofenchone (3), endo-5,6-trimethylene-2-norborneanthione (4), 3,3-diethylbicyclo[3.2.1]octane-2-thione (5), 2,2-diethyl-5,5-dimethylcyclopentanethione (6), 2-ethyl-2,6,6-trimethylcyclohexanethione (7), and 2,4,4-trimethyl-3-hexanethione (8)) are reported. Photolysis in solution typically gives rise to products arising from insertion into β, γ, and, in one case (4), δ carbons to form cyclic thiols. This chemistry is analogous to that observed in earlier studies. Novel photochemistry is found in the gas phase where Norrish type II products are also isolated from several substrates (1, 2, 5, 6, and 7). The effect of the quencher gas, butane, on both the spectral and photochemical properties of 2 in the gas phase provide evidence to support the proposal that the Norrish type II chemistry arises from initially populated vibrationally excited levels of S2.
Linearly Fused vs Bridged Regioselection in the Intramolecular 1,3-Diyl Trapping Reaction
Masjedizadeh, Mohammad R.,Dannecker-Doering, Ingeborg,Little, R. Daniel
, p. 2742 - 2752 (2007/10/02)
The intramolecular diyl trapping reaction can now be used to obtain synthetically useful quantities of either bridged or linearly fused cycloadducts in a selective manner and by design.Bridged cycloadducts arise by intercepting the triplet diyl, while linearly fused products can be produced from either the singlet or the triplet.When an electron-withdrawing group is attached to the diylophile , the singlet diyl leads selectively to fused cycloadducts.On the other hand , the presence of a large alkyl group attached to the internal carbon of the diylophile affords bridged cycloadducts selectively from cycloaddition with the triplet.Four diazenes, 4-7, differing only in the electronic and steric properties of the substituent located on the internal carbon of the diylophile, were studied.The diyl trapping reactions were conducted using ca. 1 mM solutions of diazene in THF at reflux for periods of 3-4h; cycloadduct yields ranged from 68percent ( beginning with the dimethyl ketal 7) to 98percent ( from keto diazene 4).To determine the origin of the bridged cycloadducts, the effect of oxygen upon the product distribution was examined.The results show that the rate of the intramolecular triplet diyl cycloaddition is slower than the rate of the intermolecular reaction of the triplet with oxygen.The rate of triplet intramolecular cycloaddition can be estimated to be less than 4 x 106 to 4 x 107 s-1.
